Ester-lactones of isopropenyl acetate heteropolymers



the heteropolymer t t jleic anhydride with a .monoliydric alcohol to regroups, and form the lactone derivatives.

patented s ept. l3, 194

' 'ESTER-LACTONES OFISOPROPENYL ACETATE HETERQPOLYMERS Louis M. Minsk and William 0. Kenyon, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester Jersey N. Y., a corporationoi New No Drawing; Applicationf November 27, 1945,

Serial N0. 631,214

3 Claims. (on. ain) This invention relates to resinous ester-lactones and to aprocess for preparing'the same. More particularly, it relates to ester-lactones which are prepared from the resinous heteropolymers; of isopropenyl acetate and certain unsaturated alpha, beta-dicarboxylic acid anhydrides, esters and other derivatives thereof. v

M It is known that vinyl compoundssuch as vinyl acetate and styrene are homopolymerizable to high molecular weight resinous compounds, and that they can also be polymerized with unsaturated compounds, for example, maleic anhydride, esters and other derivatives of maleic, fumaric, citraconic and mesaconic acids. In contrast, isopropenyl acetate is neither a vinyl compound nor homopolymerizable to a high "molecular weight resin] Furthermore, unlike vinyl acetate and styrene, isopropenyl acetate will not copolymerize to high molecular weight compounds with citraconic acid, its esters or anhydride or with mesaconic acid and esters. However, as disclosed in copending application Serial No. 631,215 (now United States Patent 2,452,165,

dated October 26, 1948), in the name of Cornelius C. Unruh and William O. Kenyon, isopropenyl acetate can be heteropolymerized to'high molecular weight resins with maleic 'anhydride, and esters of maleic and'fumaric acids.- We have found that by treating such heteropolymeric resins of'isopropenyl acetate and maleic anhydride, or isopropenyl acetate and esters of maleic or fumaric acid, with primary alcohols, there are obtained the corresponding esterlactone resins which constitute the compounds of our invention. The latterare highly suitablefor the'preparation of molded objects, and in certain species, for the production of'coatings and sheet materials possessing good clearness, flexibility and strength. Suitable alcohols include members which are liquids at about room temperature, for example, alcohols having up to 12 carbon atoms'in a straight chain, but preferably for higher flexibility,

alcohols having from 5 to 1-2 carbon atoms in the chain.

.Our new ester-lactone resins can, be prepared by a process comprising t1eating, .for example,

of isopropenyl acetate and mamove acyl groups, esterify acid or anhydride The reaction is-facilitated by the presence of a catalyst such as sulfuric acid or its acid equivalent. I-lydrochloric acid can be employed instead ,of

sulfuric acid. The catalyst accelerates notonly i 1 WW 9. iq m i an hi ithe l i ifi ati nfan t 2 t V t deesterification reactions as well." While the re-'- action'is carried out preferably in the absence of water,an'aqueous condition can be employed, if a highercarboxyl group content is desired. Because of the inherent difiiculties of determination, thestructure of our resins has not been completely defined, butoneof the possible formulations-is as follows: I a

[n.iiiifih] (to wherein R represents an alcohol radical or group and--11, indicates repetition'of-the fundamental group. Our new compounds are in fact resinous esters-of monohydrio alcohols and the lactones bfheteropolymers of isopropenyl alcohol and unsaturated unsubstituted alpha-beta-dicarboxylic 'acids.- i

The new e'ster-lactone resins above defined differ structurally. but little from related vinyl acetate-maleic anhydride heteropolymers. However; in their chemical and physical behavior, these differences of the two series of resins are quite significant. For example, in the preparation of our resins more drastic reaction conditions arenecessary than with the vinyl acetate- --ma1eic anhydride heteropolymer to obtain the same degree of esterification and lactonization. Thus for :the preparation. of our. butyl-lactone resin, thev sulfuric acid hadto be increased about fivefold for complete reaction, over that required for complete conversion .of the corresponding vinyl acetate-maleic anhydride heteropolymer to the ester-lactone. Similarly, isopropenyl acetatefumaric acid'esters' reacted slowly, whereas corresponding 'vin'yl acetate fumaric acid esters lactonized rapidly under similar conditions. Dliferences-existalso in the fiexibilityof the products of the-two series of resins. The 'alkyl-ester-lactones. of the isopropenyl acetate-maleicanhydride heteropolymer give brittle products, when the carbon chain length of the alkyl group is less thanfive, but flexible products, when the chain length isfive" or greater. In comparison, the butyl ester lactone of the vinyl acetate-maleic anhydride heteropolymer is flexible. I 7

Thesediiierences in behavior of related series of, resins can be partly explained by the branch- ,ing of the fundamental hydrocarbon chain of therespectiveyresin types. Our new resins are branched-in the sense that methyl groups are attached to the fundamental chain at regular in- .tervals, that is, they are part ofthe isopropenyl radical, whereas the vinyl acetatamalgaic anl iy-v branched.

' lactones was '75 grams.

ing to theory. A similar cntrated sulfuric acid -ciliitated in the dride heteropolymer by the same definition is un- In resin chemistry, this type of branching leads to a difference in properties best exemplified by the acrylate and methacrylate resins. As iswell-lgnqwn, the former are soft and elastic, easily sa'pbnified and 'rleesterified, while the latter are hard and brittle, diificult to saponiv. to reesterify. In view of the preceding and the fact that isopropenyl acetate-malei'c ar ydride heteropolymer yields a flexible ester -lactonaonly when an amyl group, the conclusion seems-warranted that the and in the polymeric acid form, also difiicultgroup or terreplase th heir}.

individual properties of a film base such as flexi;

bility, tensile strength and dimensional stability under stress, moisture and temperature are eaelr a contribution of a specific portionbf the; resin, molecule in relation to other specific portion's'of the same molecule. Accordingly, our new esterconstitute a sefies of resins having distinctive chemi al a d hys cal characteristics. It is:anobject of our invention, therefore, to provide new ester-,lactone resins. A turther ob; jec't oi the invention is to provide a process for preparing such ester-,lactone resins. Other ob; iects .will become apparent hereinafter.

The following; examples will serve to illustrate our new ester-lactone resms and the manner 9; their preparation.

EXAMPLE I.- I-In'rEROPoLYMEaIzATIqN OF IsopnoeENYL Apnra'rn, ailpwMatErc ArmYnnrnr: 5&8s 5.1 8 i a e a h d idewste dissolved in 60 gramsiofi mole) or isoprop nyl acetate and 0.12 gram I- taw rox e, were added. The reaction flaskfitted with areflux condenser and heated with contents on a steam bath with occasionalstirring. When the temperature reached the boiling point of the so; pr pem'l acetate. a vi o ous re ion 90 la and the mixture. set to, a clea alm st olo less resin. This was coole and d s ersed; n acetone- The resulting dope was poured into benzenev to pr pi at t e'polyme and the latter leached with fresh benzene and dried at 60?: C. If-he. yield The. specific viscosity oi the poly,- mer in acetone was 0.061. Analysis of the prod;- uct showed 49.? per cent by. weight maleic anhy: dride' compared :to 49.5 perjcentbyweight accQlBdproductwas! obtained by carrying the reaction-out in acetone in. the presen'c'e of hydrogen peroxide catalyst, precipitating and washing thelproductin benzene and drying at 60 C' I. 7

EXAMPLE IL-ETHYL ESTERr-I ACTQ E. 0x159? .0:

, PENYL ACETATE-MALEIC. Annrnarng.

eonYMER 125'grams (0.63 mole) of isopropenyl. acetatemaleic anhydride 'hetero'polymer. prepared. in the.

manner of Example I'were heated. with 1500.00. (25.5 mole) of absolute ethyl alcohol ona steam loath to a clear solution. "To this wasadded-with stirring a solution adjusted to "60 C. and consisting of a mixture of 209 cc. (3.5 mole) ofconand-50l (:0. (8.5; mole) of absolute ethyl alcohol. The reaction "mixture was heated on asteam bath'f-or a tenor; of 24 hours, which resulted-in the product b'eing preand pouring off the excess liquid; the-1 cake was dissolved in one liter of acetonefand then"repreci'pitated by pouring the do'pejin affine stream, withstirring' into distilledwalter. The precipitate'w' as' washed-free of acid with disftilled' w-ater form of a cake. "flAgfter coolingand dried at 50 unaccounted for.

. ROLYMER- of 'thelcolor from tone was grams. The analytical data are given in Table 1.

T-here remains a different of but 3.5 percent group present in the molecule However, the analytical data meat eh dr de een s re ie Ex ivtPLE III.

" E X J Mem Me EQF YF Y .2 g am 9-6.3; mole). maleic. anh dride 500 9, (1 mole). Qf erma Q sQpmbenn acetate? he eropp mer we e heetedw th bli yl 'el ehqlans a cat ly c, (3.51114...) 0.5 conc ntra efi shl w e @9 91 n. 59 ee 51%.. mole); of: n ma butr alqehe added. iq qw n n ene althe p wlv re oi samnle yield Qfbuty ester-lac ate wa r ms s eci ic vise txwa .0.92

end h a id ty 9 5 i-no ma rea entiper exam. equ al nt. to. 3:36pm e t or combined ma eic a d... Coatin s from compositiqn mured at iaflfi fihilitr pade 1. ms amen, lo ationfot 6; percent at hielsnesa 0i. wiltch W enm ed a 10920; he fihn-sweteb itt e hlxaivienn IVs-Harm E-srm -Lacrona or isolato PENYL. AcErArE-Matmc Aunvmims Harem;

sg r enyl ac ate;-

1-25 grams (Ofigmoley olymer were dissolved'jin ele eib. eeli r de a 99' ca 2. ee s). i

tln e ix u e n: a S

bath. To this s iiur s a a d; 0 .0; ce- (1 11': e.) cinema hexyl alcohol. The rea' tior mixture was then eeetea nesie m. at i p whichl'resulted in t e preci wi njf a h qn o res le?? e bv i V I the product. The res ousprecipitate was then redissolved i;;j -'i200- emf-atec pi a e in 5 93 wh extracted several times methyl alcohol;

distilled "wat'erfi "Phe 'fibrous f product was "ob-V;

C. The yield of the ester-lac- The coated film was brittle.

Thi-s'hiay be due to hydroxy-l from unit which j remained unlactonizedat rthe initial hydrolysis of theacet'ateradical on the isopropenyl nucleus. indicates that@. compound was obtained which was substantially the ethyl ester-'lactone' o'f is'opropenyl'acetate of; 4.; folds. a breakin h n. lsehg by r a. Period orzrhpurs. P Q o he as 7 fills rod ctf eprecipitated in 6 liters, of methyl alcohol and r malam anh d ide hefi remlymez V calvin al ewin th t9 cm! and p ng the fi m irqm. the sunfe ec,

in 236 cc. (2.0 mole), 0 ieyel he me 9n afiteazl} h ve. Asomiien 9f 3 c (Q ma e) cf fiancee: tmted'sulfuric acid and at! ca. e cyele eamql was added. After .23 heme kxeatm an Elee eteam bath. the em; nrecini axted in the term. ii a. bmwe cake. The u ernatant, li uid. was. PQQIBQ 11 ,the cake. dissolved 1.1. 390' c eeetcne n SQDEQQEi tamed am. hree lite ze Qt eheel te film echel- "Ehe, nree pitate. was. ex ract d; with Ewe 5 K ef abscm ee hyl alcenel-anql xecnsselved in ac e, She aqe eee iisner ce we then name in aifine stream mm theee l fiexe cf clistiilcq when will. stir in am; th le mined as a, white. men. Thi wee-weaned we mix; Qistilled water. centri u d. n?! d ies; at 50 Q The. i sl @i EEQQQQE wa me aw- Anal sis showed, {SEQ-ti by weight c eeetsz am} aime aeisli g e uiv?- lent to 9.98 per cent by weight of malei c a 1 While cur new eet magnqne re ns a e, viable vfie; melding purpoe w 1 hese memneze twine an ester group with a, straight chain mi at; least ive cex n. e s, il s ra e in r ex me with jamYland hezy s e eqtc s, proeuce iexime cca i g and sh s em the 6 la stici pg agents; It willbe understood, howevelf that the, more brittle members will also become g xi ie 1 y gqmqn Of plasticizers. Lamiw ich giv sh e s i able for ma f harqnesg f guy resins as relatedtg fi e ength Qt t e am er; chain of the e er em p i lqstrat q in. th f llowing; bl 1L wherein ar 51mm tes s on sim afly pmper d emp $492 m l ed. hutto e- 1 Tab e I1- ..EMQQ I scratch Ethyl esterLactone Resin Bg t yl ester-Laetorge Resin, Hexyl est erfihaetene Resin fillers added. i desired! nd' hen knee ledb l ed o: drawn ungee L rm l qr-heated eempreseed cqn itione- 91;: new meme e se he. as: fo me into u eful films end'eheeteh making solu ion of the resin. i e e lventl men cas ng th soleti n Qu .iihnrio miene ex-f ce each ewes; 9 meta pla e a swee e r sqluiiisli s. QI? 9w resins can; a so be xfimsiesi he mm of fin thread into a drying atmqeehexe c! a 92cm hat re in cmamm 0-55! 1 'me xiel with ixom the xesenee at e916 cf: snlnhuzie acids than c imes.

a w 7 en 79?? 9f. whgh meic l wlnef, a.

r Benzxl phtnalatei zlienzyl succinatcr :Q. Y ;c fiumxyethyl netmhxdmiumete 'nutyl phthalate I Campus; i e Gmonexyl acetate 7 methylene lycol mpnqhutyl. 9b niehh eneely el @li uwm e V Ethqmethxl @Qipate Ethoxsretml sebacete Eth l Pll hfilfi' V 1, Ethylene elyecl. mam "9W1 e er '1 i me ncxyethyl e ater r T =1fimhydrcf3fiuzvl asilpate mimet c nmmpiqn n mam?! enes hate 1:

mum; nhespnm i iem lene lyecl. el etetc I. z fl c h eneny phesnhete lzihmme 12mm;

' Other m: mxmal h xyl 341991301 in the pnur e qlcla wne ewnexyl eg er actene cm. csurs;

2,43, glzocess t9: nnepaiing a. z einbus. esn Q Q A- ecu air grqp mon cf the eq imela haters!- polymex oi' ,iec mfqpeny i aceie e jmaleicfapimqlec gl 'p qpb rtip e iu ic acid, wneneby amyl' egten-leetez efqrmatien 2 .9 25. m 1. 91 .91, ix;

the me sa .9;

'13.. A ergce i9; 9 39198 321? a. ice-2 9115 et'ex mqr ma nmp tism 9i 'eq imql ne g lwfl sa lem eenyl' a etate am a c mpquz i eeleehesl illqm. the. erg-up ecneistine 0:1: m ig ani- 11 1 11111121. a d l llsyl me eart wher each. 94 .122

bm lame and ialliy fumarete whe ein cl alka i. emu!) is wane ae c teing names er a. aturated .conelst ng; at e lpn ri c d an hy ro acid, whereby ester-lactone formation occlllis.

4. A process for preparing a resinous ester comprising heating to reacting temperature 1 :2s"memmxmeakmmeregetmg: temexmeeigm W modifyingagents, such'ias nep diying en s, drying 'oils', semi-drying oils, natural resins,

be admixed with our) egte lgu Qx 'sing heati g 9c reac ing emp etu te {we r I r ml'. 29 4" cam l; atcmei im flmmc 2 m 25 molequ anprgmo b qric al phati gesincus; ,ggfe r I 9 molecular proportion of the equimolar heteropolymer of isopropenyl acetate and maleic anhydride, with from 2 to 25 molecular proportions of a saturated primary monohydric aliphatic alcohol containing from 5 to 12 carbon atoms, in the presence of sulphuric acid, whereby esterlactone formation occurs.

6. A process for preparing a resinous ester 7 comprising heating to reacting temperature one molecular proportion of the equimolar heteropolymer of isopropenyl acetate and a dialkyl fumarate wherein each alkyl group is saturated and contains from 1 to 4 carbon atoms, with from 2 to 25 molecular proportions of a saturated monohydric aliphatic alcohol containing from 1 to 12 carbon atoms, in the presence of sulphuric acid, whereby ester-lactone formation occurs.

7. A process for preparing a resinous ester comprising heating to reacting temperature one 10 molecular proportion of the equimolar heteropolymer of isopropenyl acetate and diethyl fumarate, with from 2 to 25 molecular proportions of ethyl alcohol, in the presence of sulphuric acid, whereby ester-lactone formation occurs.

8. The resinous ester obtained by the process of claim 3.

LOUIS M. MINSK.

WILLIAM O. KENYON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,306,072 McNally et a1 Dec. 22, 1942 2,396,785 Hanford Mar. 19, 1946 

